Water soluble graft copolymers and methods of use thereof

ABSTRACT

A water soluble graft copolymer useful for dewatering wastewater having the structure: ##STR1## wherein E is the repeat unit obtained after polymerization of an α,β ethylenically unsaturated compound the molar percentage of a:b is from about 95:5 to 5:95 with the proviso that the sum of a and b equals 100%; G comprises the structure: ##STR2## wherein d is a cationic monomer, R 1 , R 2  and R 3  are the same or different and are hydrogen or a lower alkyl group having C 1  to C 3 , F is the salt of an ammonium cation and the molar percentage of c:d is from 95:5 to 5:95 with the proviso that the sum of c and d equals 100%.

FIELD OF THE INVENTION

The present invention pertains to novel water soluble graft copolymerswhich are useful for water ireatment, such as sludge dewatering andwater clarification. In addition they are also effective as retentionand drainage aids in the paper making process.

BACKGROUND OF THE INVENTION

There is an increasing usage of water soluble polymers and copolymers inwastewater treatment industries. These compounds have shown desirableutility for the purpose of dewatering sludge and clarifying contaminatedwater.

The efficacies of the polymers or copolymers used will vary dependingupon the type of monomers chosen to form the polymer or copolymer, themolecular weight of the synthesized molecule and, in the case of acopolymer, the placement of the selected monomers on the backbone of thecopolymer. It is the latter characteristic that is the focus of thepresent invention.

Polymers with long sequences of two monomers can be categorized as blockcopolymers or graft copolymers. In graft copolymers sequences of onemonomer are "grafted" onto a "backbone" of the second monomer type,##STR3##

Graft copolymers have unique and highly desirable properties as comparedto random copolymers or the blend of two homopolymers. Therefore, thereis a great interest in preparing them. Few techniques described in theliterature satisfy the need.

Furthermore, with ever increasing usales of water soluble polymers andcopolymers in industries such as wastewater treatment, cooling, boilerand deposit control, coating, textile, mining, detergency, cosmetics.and paper, etc , there is an urgent need to synthesize novel watersoluble graft copolymers for this broad range of applications.

It is a further object of this invent.on to prepare distinctive watersoluble graft copolymers for water treatment applications.

U.S. Pat. No. 3,869,418 describe a graft copolymer comprising apolymeric N-vinyl lactam such as N-vinyl pyrrolidone with unsaturatedcarboxylic acids, like acry ic acid and methacrylic acid in an emulsionprocess. The resulting copolymer is not water soluble and is used foradhesive and coating applications.

U.S. Pat. No. 4,271,053 discloses quaternary ammonium graft copolymersprepared by grafting quaternary aamonium ionene-type polymeric sidechains onto a polymer backbone formed by the reaction of a difunctionalamine and an epihalohydrin or diperoxide. The polymers are differentthan the present invention.

U.S. Pat. No. 4,400,496 and European Pat. No. Application 0 356 241teach grafting acrylamide or acrylic acid with starch in the presence ofceric ions. The product has to be precipitated and separated in acetoneprior to use.

Smirnova et. al., Journal of Polymer ;cience, Vol. 29, pp. 139-145describe a graft copolymerization of methacrylic acid withpolycaproamide by the persulfate/sulfite redox system in the presence ofcopper ions. It is a different reaction mechanism and results in adifferent copolymer than the present invention.

U.S. Pat. No. 4,916,191 discloses a graft copolymer prepared from amacromonomer with hydrophilic and fluorinated monomers for dispersionstabilizer in an emulsion polymerization process.

Compared to the related art disclosed above, there exists a need toprepare water soluble graft copolymers in a convenient and economicprocess. This objective is achieved by the present invention. Theresulting copolymers exhibit desired efficacy for sludge dewateringapplications.

DETAILED DESCRIPTION OF THE INVENTION

The present invention pertains to novel water soluble T graft copolymerswhich are useful for water treatment, such as sludge dewatering andwater clarification. In addition, they are also effective as retentionand drainage aids in paper/pulp making processes.

Specifically, the graft polymers in the invention contain polymericsegments obtained from the polymerization of acrylamide and cationicmonomers which are attached or "grafted" to another polymer chain whichis comprised of the repeating units of one or more monomers. Theresulting graft copolymers are soluble in an aqueous medium.

The graft copolymer of the invention has the general structure: ##STR4##wherein E in the above formula (Formula I) is the repeat unit obtainedafter polymerization of an α,β ethylenically unsaturated compound,preferably carboxylic acid, amide form thereof, alkyl (C1-C8) ester, orhydroxylated alkyl (C1-C8) ester of such carboxylic acid or sulfonicacid. Compounds encompassed by E include the repeat unit obtained afterpolymerization of acrylamide, methacrylamide, acrylic acid, methacrylicacid, maleic acid or anhydride, styrene sulfonic acid,2-acrylamico-2-methylpropyl sulfonic acid, itaconic acid, and the like.Ester derivatives of the above mentioned acids such as 2-hydroxypropylacrylate, methyl methacrylate, and 2-ethylhexyl acrylate, are alsowithin the purview of the invention.

The molar percentage of a:b is from about 95:5 to 5:95, with the provisothat the sum of a and b equals 100%.

G in the above formula (Formula I) is a polymeric segment comprisingrepeat units having the structure: ##STR5## wherein R₁, R₂ and R₃ inFormulae I and II are the same or different and are hydrogen or a loweralkyl group having C₁ to C₃ Monomer d is a cationic monomer. F in theabove formula is a salt of an ammonium cation, such as NHR₃ N⁺ R(₄,5,6)M⁻ or OR₃ N⁺ R(₄,5,6) M⁻, wherein R₃ is a C₁ to C₄ linear or branchedalkylene group, and R₄, R₅ and R₆ can be selected from the groupconsisting of hydrogen, C₁ to C₄ linear or branched alkyl, C₅ to C₈cycloalkyl, aromatic or alkylaromatic group; and M is an anion, such aschloride, bromide, or methyl or hydrogen sulfate. Typical cationicmonomers are 2-acryloyloxyethyltrimethyl ammonium chloride (AETAC),3-methacrylamidopropyltrimethyl ammonium chloride (MAPTAC),2-methacryloyloxyethyltrimethylammonium chloride (METAC) and diallyldimethylammonium chloride (DADMAC), etc.

It is to be understood that more than one kind of cationic monomer maybe present in Formula II.

The molar percentage c:d in Formula II may vary from 5:5 to 5:95, withthe proviso, however, the sum of c and d equals 100%.

There is no limit to the kind and mo18 percent of the monomers chosen solong as the total adds up to 100 mole % and the resulting copolymers arewater soluble.

At present, the preferred water soluble graft copolymer for use insludge dewatering is: ##STR6##

The molar percentage of a:b is from about 95:5 to 5:95, with the provisothat the sum of a and b equals 100%. G in Formula III is: ##STR7##Monomer d is 2-acryloyloxyethyltrimethyl ammcnium chloride (AETAC). Themolar percentage c:d in the polymer segment G (Formula IV) is the ratioof Acrylamide:AETAC. It may fall within the range between 95:5 and 5:95.The sum of c and d must add up to 100%.

The number average molecular weight (Mn) of the polymeric segment G isnot critical and may fall within the range of 1,000 to 1,000,000.Preferably, the number average molecular weight will be within the rangeof 5,000 to 500,000, with the range of about 10,000 to about 200,0DObeing even more desirable. The key criterion is that the resulting graftcopolymer be water soluble.

The graft copolymer is prepared via a two-step polymerization process.First, a macromonomer comprised of acrylamide and AETAC is prepared by asolution polymerization method using peroxide as an initiator. Theinitiator may be selected from peroxides, persulfates, bromates, andazo-type initiators such as 2,2'azobis-(2-amidino-propane)dihydrochlo.ide, 2,2'-azobis-(2,4-dimethylvaleronitrile). Copper (II)sulfate is added in the process as an oxidative chain transfer agent togenerate a terminal unsaturated double bond in the polymer chain. It isconceivable that transition metal ions other than copper, such as iron,cobalt, and nickel etc., may be used in the invention.

Ethylenediamine tetraacetic acid or dlethylenetriamine pentaacetic acidand their salts are used as chelating agents to chelate copper prior tothe second polymer zation step.

The resulting macromonomer is then ccpolymerized with acrylamide orother monomers to form graft ccpolymers by a water-in-oil inverseemulsion technique. Such processes have been disclosed in U.S. Pat. Nos.3,284,393, Reissue 28,474 and Reissue 28,576, herein incorporated byreference. The resulting copolymer may also be further isolated byprecipitating it in an organic solvent such as acetone and dried to apowder form. The powder can be easily dissolved in an aqueous medium foruse in desired applications.

Branching agents such as polyethylenellycol di(meth)-acrylate, methylenebis(meth)acrylamide, N-vinyl acrylamide, allyl glycidyl ether, glycidylacrylate and the like may also be added, providing the resulting graftcopolyme is water soluble. Any of the well known chain transfer agentsfamiliar to those who skilled in the art may be used to control themolecular weight. Those include, but are not limited to, lower alkylalcohols such as isopropanol, amines, mercaptans, phosphites, thioacids,formate, allyl alcohol and the like.

Conventional initiators such as peroxide, persulfate, along withsulfite/bisulfite and azo compounds may be used depend on the systemchosen.

High HLB inverting surfactants such a: those described in U.S. Pat. No.28,474 are then added to the emulsion to convert the resulting emulsionto a "self-inverting" emulsion. Using the procedure described herein, aunique graft copolymer in emulsion form is obtained.

It is to be understood that the aforementioned polymerization methods donot in any way limit the synthesis of copolymers according to thisinvention.

The resulting emulsion disperses and dissolves rapidly into an aqueoussolution upon addition to water. Within minutes, a maximum solutionviscosity is obtained. The emulsion dissolves well even in watercontaining a high level of hardness and it also retains most of itssolution viscosity in brine water.

The structure of the graft copolymer is substantiated by a conventionalsolution viscosity study and C₁₃ NMR spectroscopy. The molecular weightof the resulting graft copolymer is not critical, as long as it issoluble in water. The molecular weight may vary over a wide range, e.g.,10,000-30,000,000 and may be selected depending upon the desiredapplication. The invention finds its greatest usefulness in sludgedewatering when the acrylamide copolymers have molecular weights inexcess of 1,000,000.

EXAMPLES SYNTHESIS OF GRAFT COPOLYMERS Example 1-3 Synthesis ofMacromonomers

5 To a suitable flask equipped with a condenser, a thermometer, anitrogen inlet, and an overhead agitator was charged with the desiredamount of reagents as shown in Table I. The solution was adjusted to pH5.1 and then cooled to 15° C. After the solution was sparged withnitrogen for 3C minutes, a tertbutyl hydroperoxide solution was added toit. Exotherm started immediately and the reaction temperature increasedcorrespondingly. The polymerization was terminated by purging with airinto the solution and by the addition of EDTA 2Na solution after acertain period of reaction time.

                  TABLE I                                                         ______________________________________                                        Synthesis of Macromonomers                                                                    Example   Example  Example                                    Reagents Charged                                                                              1         2        3                                          ______________________________________                                        Acrylamide (53% in water)                                                                     100.70    196.62   228.15                                     AETAC* (79,2% in water)                                                                       173.61    181.58   129.98                                     CuSO.sub.4 5H.sub.2 O                                                                         0.038     0.055    0.055                                      D.I. Water      101.31    108.29   77.40                                      t-BHP** (2.2% in water)                                                                       5.43      8.07     8.71                                       EDTA 2Na***     50.00     75.00    75.31                                      Mn X 104****    5.5       4.2      3.1                                        ______________________________________                                         *AETAC = 2acryloyloxyethyltrimethyl ammonium chloride                         **tBHP = tertbutylhydroperoxide; 70% active                                   ***EDTA 2Na = disodium ethylenediamine tetraacetate                           ****The number average molecular weight of the polymers was determined by     gel permeation chromatography.                                           

Example 4-6 Synthesis of Graft Copolymer--Redox Initiation

Graft copolymers were prepared by copolymerizing the macromonomers ofExamples 1 to 3 with acrylamide by an inverse emulsion polymerizationmethod. The polymerizations were carried out in a similar apparatus asthe Example 1. The oil phase was composed of sorbitan monoleate, oleicisopropanolamid and a low volatile aliphatic oil (LOPS.sup.®). Theaqueous phase contained acrylamide, ammonium chloride, water, and one ofthe macromonomers from Examples 1-3. The aqueous phase was thentransferred to the oil phase and the mixture was homogenized to obtain astable emulsion. The resulting emulsion was then sparged with nitrogen.

The polymerization was carried out by adding the aqueous solution ofsodium metabisulfite (SMB) into the emulsion to react with the t-BHPthat remained in the macromonomer solution. About 15 g of 1.1% SMBsolution was added over a period of time of 3 hours. The polymerizationtemperature was controlled to a maximum of 40C. After the addition ofSMB solution was complete, additional t-BHP and 30% SMB solution wasslowly added to react with the residual monomers. High HLB surfactantswere then slowly added to the emulsion to obtain a self-invertingemulsion. The reagent charges and the intrinsic viscosity of theresulting graft copolymers are shown in Table II.

                  TABLE II                                                        ______________________________________                                        Graft Copolymerization (by inverse emulsion polymerization)                                Example  Example  Example                                                                              Example                                 Reagents Charged                                                                           4        5        6      7                                       ______________________________________                                        Sorbitan monooleate                                                                        3.78     3.78     3.78   3.77                                    Oleic isopropanolamid                                                                      3.78     3.78     3.78   3.78                                    LOPS ®   105.63   105.13   105.27 100.12                                  Vazo 52      --       --       --     0.083                                   Acrylamide (50% in                                                                         189.64   160.64   131.11 160.62                                  water)                                                                        Ammonium Chloride                                                                          13.52    13.50    13.50  13.52                                   Makeup Water 35.99    33.20    36.20  33.69                                   Example 1    94.60    --       --     --                                      Example 2    --       120.55   --     120.68                                  Example 3    --       --       147.94 --                                      Sodium Metabisulfite                                                                       0.17     0.18     0.17   --                                      (SMB)                                                                         D.I. Water   15.07    15.10    15.20  --                                      30% SMB Solution                                                                           7.95     8.00     8.10   8.10                                    Aerosol OT   2.81     2.77     2.78   2.66                                    Tergitol 15-S-9                                                                            9.41     9.29     9.31   8.90                                    Emulsion Solids %                                                                          35.0     34.4     33.5   35.8                                    Intrinsic Viscosity                                                                        7.0      8.5      9.9    10.0                                    (dL/g)                                                                        ______________________________________                                         Aerosol OT = dioctyl ester of sodium sulfosuccinic acid, American Cyanami     Tergitol 15S-9 = CIIC15 secondary alcohol ethoxylate, Union Carbide           LOPS  ®= low odor petroleum solvent, Exxon                                Vazo 52 = 2,2,azobis (2,4dimethylyaleronitrile), DuPont                  

Example 7 Graft Copolymer Synthesis--Thermal Initiaticn

The apparatus, procedure and reagents similar to that described inExamples 4-6 was used except that this time, a thermal initiator, Vazo52 was chosen. The polymerization was carried out at 40° C. for 3.5hours and then at 45° C. for 2 more hours. After the polymerization wascomplete, high HLB surfactants were added to convert the emulsion into aself-inverting emulsion. The reagent charges and the intrinsic viscosityof Example 7 are shown in Table II.

PERFORMANCE TEST

In the following tests, the performance of the resulting water solublegraft copolymers described in this invention is demonstrated. ACapillary Suction Time (CST) device was used to measure the dewateringperformance of the various polymers on several different substrates. TheCST device consists of an electronic timer, a plexiglass cell holdercontaining two concentric electrodes, and a tall stainless steelcylindrical cell. The device operates by measuring the drainage of waterfrom a sludge substrate out of the cell. This is accomplished by placingthe cell holder containing the two electrodes on a piece u of Whatman#17 chromatography paper, 7.0×9.(cm in size. The tall cylinder is thenplaced in the hole in tte cell holder. The cell holder is connected tothe electronic timer, which is turned on and reset. A 7 ml aliquot ofthe substrate is introduced into the cell. As the water migrates out ofthe cell, it is absorbed onto the chromatography paper. This results ina migration of a water front through the paper. As the water advances,it contacts the first electrode, activating the timer. Continuedadvancement of the water eventually reaches the second electrode,completing the circuit and shuttinl off the timer. The process isrepeated for several polymer dosages. A dosage response curve plottingCST time (in seconds) versus polymer dosage gives an indication of aparticular polymer's effectiveness in dewatering a substrate. The dosagecurve minimum is an indication of the optimum polymer dosage, while theextent of the trough gives a measure of the polymer,s tendency tooverdose. Overdosing is observed when the CST values increase withincreasing polymer dosage. Generally, the trnatment which produces thelowest CST value at the lowest dosage is the most effective.

A sample of mixed primary and secondary sludge from a paper mill wasused as the test substrate. The graft copolymer performance was comparedto a commercial copolymer containing similar mole % of the cationicmonomer used for this type of application. The copolymers were added tothe water system to be treated in an amount sufficient to mainiain aconcentration, based on active polymer, of from about 10 ppm to 1000ppm.

Dewatering performance is presented in Table III.

                  TABLE III                                                       ______________________________________                                        Dewatering Performance                                                        Sludge pH = 6.14                                                                             Total Solids = 2.04%                                                         Polymer Dosage                                                                             CST                                                Treatment     (ppm - Active)                                                                             (Seconds)                                          ______________________________________                                        Blank         --           173.2                                              Polymer A*    37           113.4                                                            74           48.2                                                             111          24.6                                                             129.5        37.1                                                             148          25.6                                                             185          15.2                                                             222          15.3                                                             259          15.5                                                             296          13.1                                                             370          38.9                                               Example 4     17.5         73.5                                                             35           37.6                                                             70           14.4                                                             105          17.9                                                             113.8        19.4                                                             122.5        12.4                                                             131.3        18.8                                                             140          21.5                                                             175          19.0                                                             245          24.4                                                             315          33.1                                               Example 5     34.4         62.3                                                             68.8         30.3                                                             103.2        15.2                                                             120.4        16.0                                                             137.6        15.9                                                             172          14.9                                                             206.4        18.3                                                             240.8        14.1                                                             275.2        18.9                                                             344          34.1                                               Example 6     33.5         59.9                                                             67           37.7                                                             100.5        34.4                                                             117.3        16.7                                                             134          9.6                                                              150.8        13.7                                                             167.5        10.0                                                             201          13.3                                                             234.5        15.6                                                             268          22.3                                               Example 7     35.8         86.2                                                             71.6         30.1                                                             107.4        19.0                                                             143.2        15.8                                                             161.1        14.7                                                             179          14.4                                                             214.8        11.5                                                             250.6        14.6                                                             286.4        17.7                                                             358          25.7                                               ______________________________________                                          *Polymer A = A commercial AMD/AETAC copolymer in emulsion form with an       intrinsic viscosity of 14 dL/g and 37% solids.                           

The above data show that the graft copolymers in this invention are moreeffective in sludge dewatering than the commercially available materialwhich is a random copolymer.

While this invention has been described with respect to particularembodiments thereof, it is apparent that numerous other forms andmodifications of this invention will be obvious to those skilled in theart. The appended claims and :his invention generally should beconstrued to cover all such obvious forms and modifications which arewithin the true spirit and scope of the

We claim:
 1. A method of dewatering wastewater comprising adding to thewastewater from about 10 ppm to about 1000 ppm, based on active polymer,of a water soluble graft copolymer having the structure: ##STR8##wherein E is the repeat unit obtained after polymerization of an α,βethylenically unsaturated compound, the molar percentage of a:b is fromabout 95:5 to 5:95 with the proviso that the sum of a and b equals 100%,G comprises the structure: ##STR9## wherein R₁, R₂ and R₃ are the sameor different and are hydrogen or a lower alkyl group having C₁ to C₃, Fis the salt of an ammonium cation and the molar percentage of c:d isfrom 95:5 to 5:95 with the proviso that the sum of c and d euqals 100%.2. The method of claim 1 wherein the ethylenically unsaturated compoundis selected from the group consisting of (a) an ethylenicallyunsaturated carboxyilc acid, the amide form thereof, the alkyl (C₁ -C₈)ester thereof, the hydroxylated alkyl (C₁ -C₈) ester thereof andethylenically unsaturated sulfonic acid.
 3. The method of claim 2wherein the ethylenically unsaturated carboxylic acid is selected fromthe group consisting of acrylamide, methacrylamide, acrylic acid,methacrylic acid, maleic acid, maleic anhydride, itaconic acid,2-hydroxypropyl acrylate, methyl methacrlate and 2-ethylhexyl acrylate.4. The method of claim 2 wherein the ethylenically unsaturated sulfonicacid is selected from the group consisting of styrene sulfonic acid and2-acrylamido-2-methylpropyl sulfonic acid.
 5. The method of claim 1wherein F is selected from the group consisting of NHR₃ N⁺ R(₄,5,6)M⁻,wherein R₃ is a C₁ to C₄ linear or branched alkylene group, R₄, R₅ andR₆ are selected from the group consisting of hydrogen, C₁ to C₄ linearor branched alkyl, C₅ to C₈ cycloalkyl, aromatic or alkylaromatic grup,and M⁻ is an anion selected from the group consisting of chloride,bromide, methyl sulfate and hydrogen sulfate.
 6. The method of claim 5wherein the cationic monomer is selected from the group consisting of2-acryloyloxyethyltrimethyl ammonium chloride,3-methacrylamidopropyltrimethyl ammonium chloride,2-methacryloyloxyethyltrimethyl ammonium chloride and diallyl dimethylammonium chloride.
 7. The method of claim 1 having the structure:##STR10## wherein the molar percentage a:b is from about 95:5 to 5:95 ,with the proviso that the sum of a and b equals 100%, and G has thestructure: ##STR11## wherein the molar percentage of c:d is from 95:5 to5:95 with the proviso that the sum of c and d equals 100%.
 8. The methodof claim 1 wherein the number average molecular weight of G is fromabout 1,000 to about 1,000,000.
 9. The method of claim 8 wherein thenumber average molecular weight of G is from about 5,000 to about500,000.
 10. The method of claim 9 whereir the number average molecularweight of G is from about 10,000 tc about 200,000.
 11. The method ofclaim 1 wherein the copolymer has a number average molecular weight offrom about 10,000 to 30,000,000.
 12. The method of claim 22 wherein thecopolymer has a number average molecular weight of from about 1,000,000to 30,000,000.